HU176873B - Herbicide composition for algae and water plants - Google Patents

Abstract

1491137 Pesticidal application of copper complexes SANDOZ Ltd 17 Feb 1975 [19 Feb 1974] 6567/75 Heading A5E An algaecide and aquatic herbicide comprises a complex of a copper (II) compound and either (a) an amine of the formula: in which R<SP>1</SP>-R<SP>4</SP> are hydrogen or C 1 -C 3 alkyl, R<SP>5</SP> is a C 2 -C 6 saturated divalent hydrocarbon radical and n is 1-5 or (b) an amino-C 2 -C 5 - alkylene-C 2 -C 5 -alkanolamine provided that when (b) is used it is complexed with an acid copper (II) salt and used to combat aquatic weeds. The complex may be sprayed or strewed on the water or added in aqueous solution or emulsion e.g. through a hose at the bottom of the water to be treated, optionally with a further herbicide or algaecide, e.g. diquat or endothal K.

Description

The present invention relates to an algae and an aqueous herbicide containing copper complexes, in particular copper (II) complexes.

Compounds of copper salts with alkanolamine or aliphatic hydroxy acids are known to have an aqueous weed or algae control (U.S. Patents 2,734,028 and 2,400,863). However, their stability is not satisfactory.

FIELD OF THE INVENTION The present invention relates to an agent for controlling algae and / or aquatic weeds in water covered by them, comprising as an active ingredient a copper (II) salt suitable for complexation and an amine of formula I and the amine and copper (II) compound molar ratio of 1: 1 to 10: 1, and the copper content of 1 to 12 times by weight ⁰ / ».

In the general formula I

R 1, R ₂ , R ₃ and R ₄ are each independently hydrogen or methyl,

B-5 is a linear or branched C 2 -C 4 alkylene group and n is an integer from 1 to 4.

If n is greater than 1, the repeat units R ₅ may be the same or different.

Generally, copper (II) salts suitable for complexation are copper (II) compounds that produce significant amounts of copper (II) ions in aqueous media. Such complexing copper (II) compounds include, for example, copper (II) hydroxide (also as copper (II) oxide hydrate); copper (II) salts of inorganic acids such as copper (II) sulfate, copper (II) carbonate, copper (II) nitrate, copper (II) chloride, copper (II) bro2 mid, copper (II) chlorate and copper (II) sulfamate [Cu (SO ₃ NH ₂ ) ₂ J; and copper (II) salts of organic acids such as carboxylic acids including mono- and polycarboxylic acids and amino acids such as copper (II) formate, copper (II) acetate, copper (II) citrate, copper (II) tartrate, copper (II) benzoate, copper (II) gluconate, i.e. simple copper salts of inorganic and organic acids, and double salts with copper (II) hydroxide, generally referred to as basic copper (II) salts, e.g. basic copper carbonate [Cu (OH) ₂ .CuCO ₃ ], basic copper chloride [Cu (OH) ₂ .CuCl ₂ ] and basic copper sulfate [Cu (OH) ₂ . .CuSO ₄ ]. Particularly valuable are complexes derived from copper (II) hydroxide, preferably acidified with an equivalent acid, and complex compounds derived from copper (II) sulfate, such as complexes derived from copper (II) sulfate pentahydrate, are extremely valuable.

In the prior art, such complexes can be prepared from copper (II) hydroxide or basic copper (II) salt, and in a further process step, the resulting basic copper (II) salt complexes are acidified with at least one equivalent acid, such as a mineral acid.

Amines of general formula I suitable for complexation include alkylene amines such as ethylenediamine, 1,2- or 1,3-propylene diamine, N-methylethylenediamine, N, N'-dimethyl-1,3-propylene diamine, N-methyl-1 3-propylene diamine, N-methyl-1,3-propylene diamine and Ν, Ν, Ν ', Ν'-tetraethylenediamine, and polyalkylene polyamides such as diethylene triamine, triethylene tetramine, tetraethylene pentamine and dipropylene triamine.

Preferably at least one, preferably two or three groups, in particular R 1 -R _4, are each hydrogen. Further, in formula I, R _{5 is} primarily two carbon atoms. R ₅ preferably form a straight chain unit, for example, - _{<CH2) m} -képletű unit, wherein m is 2-6.

In the general formula I, n is preferably 1 to 3, for example 1 to 2, in particular 1.

Particularly suitable complexing 1b amines of the general formula: - wherein R, R, R, R _and R 'are as defined above -, primarily Ic amines of the general formula: - wherein R5 is as hereinbefore defined - above all include the ethylenediamine.

It is contemplated that any mixture of amines may be used to form complexes, resulting in a mixture of complexes, or mixed ligand complexes, or both. Therefore, a mixture of copper (II) salts suitable for complexation can also be used. As defined above, the copper (II) complex compound is hereinafter referred to as the complex.

The complexes of the present invention are conveniently prepared by reaction of copper compounds with amines in an aqueous medium.

The reaction is generally exothermic, and is conveniently carried out without heating, and the addition of reagents is controlled such that the reaction temperature is, for example, below 70 ° C. Preferred stoichiometric ratios of the reagents are 1 to 10 moles of amine per gram of elemental copper (based on the copper II compound), preferably 1 to 5 moles of amine per 1 g of copper, particularly preferably 1 to 3 moles of amine per 1 g of copper . The most preferred ratio in practical terms is the complex of 2 moles of amine and 1 g of elemental copper.

A complex consisting of 2 moles of ethyleneamine and 1 g of elemental copper exhibits extremely favorable stability conditions (hanging K value of 20.03; K = dissociation constant of the complex). The complex is represented by the formula [Cu (H ₂ N-CH ₂ -CH ₂ -NH ₂ ) ₂ (H ₂ O) ₂ ] ²⁺ x A ^y ~, where A is an anion and x and y are 1 or 2, respectively. with the restriction that x and y 2.

According to the invention, the agents containing the copper (II) complexes can be used in the usual manner, for example by spraying or spraying on the surface of the water. Another application can be with a trailing horse technique.

The complexes may be used in solid form, for example, by spraying or simply dissolved in water or in formulations, and the formulations may contain such carriers, diluents and other additives as are customary for herbicides and algae pesticides.

The formulations may be solid or liquid, for example solid formulations for slow release pellets or concentrated aqueous solutions or concentrated emulsions. Suitable carriers or diluents are, for example, talc, starch, gelatin, xylene, gas oil. The formulations contain surfactants such as Aliquat (Trademark, Generic Mills, Inc., Chemical Div., Illinois, USA, Coconut Trimethylammonium Chloride), Spamate (Trademark, KDM Company, San Antonio, Texas, USA). States containing an acid amide salt of a fat) and may contain emulsifiers S-120 (Trademark, Standard Spray and Chemical Company, Lakeland, Florida, USA). Emulsifiers, in particular cationic or nonionic emulsifiers such as Spramate or S-120, can already be used together with an organic phase, such as xylene or gas oil, as an inverse phase in water-oil.

Generally, it is not necessary to isolate the complex from the reaction mixture. Thus, the resulting reaction mixture may optionally be used as an algae or herbicide in combination with carriers and diluents and / or additives after lowering the pH, for example after the addition of dilute mineral acid.

The solutions or compositions of the complexes preferably have a copper content of from 1 to 12% by weight, in particular from 6 to 10% by weight, particularly from 7 to 8.5% by weight, for example 8% by weight.

In aqueous compositions, the pH of the complex is preferably from 6 to 12, in particular from 7 to 12, for example 8 to 12, in particular 9 to 11.5, for example 10.

The complexes are preferably used in such a way that the concentration of 0.1 to 10 ppm, preferably 0.3 to 6 ppm, in particular 0.5 to 1.0 ppm, of copper in the water in which it is used is calculated.

The complexes may also be used in combination with other herbicides and algae pesticides. For example, the following active ingredients may be used: Ammate (Trademark, Inorganic Ammonium Sulphamate-containing Herbicide, E. I. Du Pont de Nourours and Co., United States), Deiquat (generic name, I.C.I. Ltd., Great Britain, organic herbicide containing 1,1'-ethylene-2,2'-bis (pyridinium) dibromide as active ingredient], salts of endothal (common name, Penwalt Corp., USA) 3 , An organic herbicide containing 6-endo-oxo-hexahydro-phthalic acid, Aquathol-K (trademarked by Penwalt Corp., USA, an organic herbicide containing a dipotassium salt of 3,6-endo-oxo-hexahydro-phthalic acid) or K-Lox (trademark, copper complex made from copper hydroxide and triethanolamine (Sandoz AG, Switzerland).

The complexes of the present invention are a variety of algae of the order of Cladophora and Spirogyra, including filamentous algae, planktonic algae such as Microcystis and Anabaena, algae known as black, brown or red algae in swimming pools and algae in lakes such as Dictyosphaerium, Oedogonium, Chlor , Pithophora, Hydrodictyon and Lyngbya.

The complexes of the present invention can also be used to control a variety of aquatic weeds, such as Najadaceae, Vallisneriae, Hydrilla, Myriophyllum verticillatum, Hyazinthae and Egeria, especially Hydrilla verticillata and Egeria densa. The agent of the present invention is preferably used to control aquatic weeds.

The agents containing the complexes of the present invention have the advantage of extremely low toxicity to fish, such as toxicity [LC ₅₀ is the concentration at which 50% of the fish die] with copper (II) sulfate pentahydrate / ethylenediamine 1: 2 complex Lepomis macrochiruson 24 or It was detected in 90 hours. Therefore, they can be used very well in fish-installed waters.

In addition, the complexes are not very corrosive and less prone to detaching elemental copper, as shown by corrosion tests on aluminum and mild steel. Therefore, they can be used in waters where machine parts such as pumps and pipes can be counted.

The complexes are remarkably stable between pH 6 and pH 12, particularly in alkaline media. Therefore, they can be used in alkaline waters, for example, at pH 7 to 11.

The following examples illustrate the invention. Percentages refer to weight percent. Temperature data is given in degrees Celsius. Specific gravity and viscosity were determined at 25 ° C. The viscosity is given in centipoise units (cP).

Example 1

Preparation of the Copper-Containing Complex Molar crystalline copper (II) sulfate pentahydrate was reacted with 2 moles of 91-93% ethylene diamine (EDA, "reagent grad", residual water). The reaction is highly exothermic. Copper (II) sulfate pentahydrate was added portionwise over half an hour at a temperature below 70 °. The dark purple solution was diluted with water until the copper content (based on elemental copper) was T '/ _o . Physical constants of the resulting solution are as follows: pH: 11.5; Specific gravity: 1.182 at 25 °; Viscosity: 13.6 cP at 25 °.

Example 2

a) Preparation of a complex solution

567 liters of water and 187.8 kg of 99% ethylene diamine (EDA) were placed in a Cowles solution vessel. The temperature of the well-stirred solution is 56 °. While stirring, 181.4 kg of crystalline copper (II) sulfate pentahydrate (100% pass through a 0.5 mm sieve, 95% pass through a 0.15 mm sieve) are added over 5 minutes. Thereafter, a total of 390 kg of crystalline copper (H) sulfate pentahydrate was added every 45 hours in 45 kg portions. The molar ratio of ethylenediamine to copper was calculated to be 1.998: 1 based on a copper content of 25.19% of crystalline copper (II) sulfate pentahydrate. The pH of the solution is 8.0. After addition of 100 liters of water and 5 kg of 99% ethylenediamine and stirring for 15 minutes, the pH is 10.6. The copper content is 8.12% and its specific gravity at 25 ° is 1.224. A total of 908 liters of product is filled into 19 liter containers. The analytical and physical characteristics of the complex solution are as follows:

Ingredients: Found: Calculated: ⁰¹ copper 8.12% 8.00% ethylene 15.24% WATER 64.67% carbon 6.48% 6.05% hydrogen 9.32% 9.28% nitrogen 7.31% 7.05% sulfate 11.13% ^ 12.08% pH 10.6 - density (25 °) 1.224 g / cm ³ - viscosity (25 °) 14.5 cP color murrey

'Calculated on an aqueous solution of 8% metal copper and 2: 1 amine: copper, calculated on a total basis of 3.71%.

The pH of the resulting solution can be adjusted to 10, including with mineral acid.

b) Preparation of a solid complex

Bis (ethylenediamine) copper (II) sulfate crystals from the complex solution can be selected in 100% yield by addition of 5 l of 5 times 95% alcohol.

The crystals were collected by filtration. The filtrate is colorless and virtually copper free. The product was dried overnight at 30 ° C in a vacuum oven.

Analytical results for copper, sulfur, carbon, hydrogen and nitrogen confirm the formula Cu (EDA) ₂ SO ₄ .

Cu (NH ₂ CH ₂ CH ₂ NH ₂ ) _{2 Found}

Calculated according to the formula SO4,% ⁰

copper 22.78 22.6 sulfate 34.33 34.5 ' carbon 17.3 16.95 hydrogen 5.77 5.89 nitrogen 20.2 19.96

“Calculated on the basis of 11.5% sulfur content.

The composition containing this substance can dispense Hydrilla aquatic weeds in ponds up to 0.5 ppm copper.

Example 3

To a solution of 133 g of anhydrous ethylenediamine (98%) in 273 ml of water is added slowly with stirring.

117 g of copper (II) hydroxide, while the copper hydroxide dissolves rapidly. The addition is controlled so that the temperature remains below 50 °. After the solids were completely dissolved, water (273 mL) was added. The resulting solution 35 was bluish purple in comparison with the dark purple color of the copper sulfate product of Example 2. After cooling to 25 ° C with further cooling, the solution has the following composition: 8.1% copper content, pH about 14, density at 25 ° C 1.138 and viscosity at 25 ° C 12 cP. To improve the stability of the solution, adjust the pH to between 9 and 11 by adding at least an equimolar amount of a mineral acid such as sulfuric acid.

Example 4

In analogy to Example 3, 102 g of copper (II) hydroxide (1 g of copper) were added to a solution of 145 ml of 91-93% ethylene 50 diamine (2 M) in 561 ml of water. The hydroxide dissolves rapidly when added to the ethylenediamine solution initially heated to 50 °. The temperature is then lowered and stirred at 30 ° for 4 hours until completely dissolved. A dark blue solution is obtained. The solution 55 has the following characteristics: 8.15% copper content, pH about 14, density at 25 ° C 1.136, viscosity at 25 ° C 14.5 cP.

The pH is adjusted to between 9 and 11 with mineral acid to improve the stability of the solution.

Example 5

In analogy to Example 1, 131 g of copper (II) sulfate pentahydrate is slowly reacted with 82 g of 90% 65-1,2-propylenediamine in an aqueous solution. The temperature of the reaction mixture rises to 69 '. After one hour, dilute with water until the copper content is 8.01%. Other features of the solution:

The corresponding copper complexes are prepared analogously from copper (II) sulfate and / or copper (II) hydroxide from diethylenetetramine, triethylenetetramine, 1,3-propylene diamine, N, N'-dimethylpropylenediamine, N-methyl-1,3-propylenediamine and tetraethylene pentamine.

Example 6

In a manner analogous to Example 5, 5.131 g of copper (II) sulfate pentahydrate is added to an aqueous solution of 96.2 g of N-methylethylenediamine. The solution was stirred for 8 hours and diluted to bring the copper content to 8.09%. The solution has a pH of 11.9, a density of 1.215 at 25 ° and a viscosity of 24 cP at 25 °.

Solutions containing 8% copper can be prepared using 2: 1 molar ethylene diamine copper from copper (II) chloride (CuCl _2. 2 H 2 O), copper (H) acetate [Cu (CH ₃ CO ₂ ) ₂ . H ₂ O], copper (II) nitrate [Cu (NO ₃ ) _2. 3 H ₂ O] and copper (II) sulfamate [Cu (SO ₃ NH ₂ ) ₂ ].

Example 7 was investigated in area la). The following solutions were used:

Area 1 (40.5 m ² ) 60.8 liters of complex solution with 1 ppm elemental copper concentration of 1233.5 m ³ , 3.6 liters of sorbitan monodate emulsifier

Area 2 2.7 m x 122 m lanes

15.14 liters of complex solution

7.57 liters of diquat (36% active ingredient)

11.34 kg Ammate

1.89 liters of S-120 (sorbitan monooleate emulsifier) dispersed in an organic gas oil phase for inverse treatment and having a copper concentration of 0.25 ppm / 1233.5 m ³ . The inverse treatment was performed with hoses which were drawn through the bottom of the water.

In all cases we found significant herbicidal activity.

Example 9

In laboratory experiments different complexes were examined on Hydrilla verticillata weed. The complexes were added in an aqueous solution containing sorbitan monoleate so that the elemental copper concentration was as follows:

Algae and weed control

Solution

Example 2 (a) of a complex

Copper content, ppm

pellet, adjusted to pH 10, in 3 aqueous areas CuSO ₄ .2 moles ethylene diamine complex 0.5 (each has a surface area of about 81 m ² and .2 mole CuSO ₄ (N-methyl-ethylene) - about 150 cm deep) with water weeds -complex 0.5 bear any liability. including water hyacinths and algae. CuSO ₄ .2 mol (1,2-propylene diamine) - The solutions have the following composition: 35 complex 0.5 CuSO ₄ .2 mol (1,3-propylene diamine) - Area 1 60.6 liters of complex solution -complex 0.5 227.0 liters of water CuSO ₄ . tetraethylene pentamine complex 0.5 11.35 liters Spra-mate 56.8 liters xylene Mix 40 Area 2 30.3 liters of complex solution CuSO ₄ .2 mol ethylenediamine 50% g 1 0.5 15.1 liters of Aquathol-K (40.3% active ingredient) Cu (OH) ₂ .2 mol triethanolamine 50% g 227 liters of water Cu (OH) ₂ .2 mol ethylene diamine complex 0.5

liters xylene liters of complex solution liters of diquat (36% active ingredient) liters of water

11.35 liters of Spra-mate

56.8

Area 3 30.3

15.1

238.4

11.35 liters of Spra-mate

56.8 liters xylene.

Each formulation was sprayed in an amount such that the copper content of areas 1, 2, and 3 was 0.5 and 0.25, respectively. and 0.25 ppm (based on elemental copper).

In all cases, 5 weeks after spraying we found significant herbicidal and algae killing effects.

Example 8

Herbicide

The complex solution prepared according to Example 2 (a), after adjusting its pH to 10.0, was infused with 3 types of aqueous weeds (including water hyacinths and HydrilA) at 2 and 4 weeks post-treatment, respectively. , especially after 4 weeks.

The CuSO ₄ .2 mole ethylenediamine complex was used analogously against the aqueous weed of Egeria densa. The herbicidal effect is significant.

Example 10

Algae killer effect

The complex solution prepared according to Example 2 (a) was adjusted to pH 10 in laboratory experiments against Microcystis aeraginosa, Lyngbya versicolor and Pithophora algae at a copper concentration of 0.01 to 1.0 ppm based on elemental copper. In all cases, algae killing activity was observed, especially at higher concentrations (> 0.1 ppm).

The solution contains xylene as carrier and Spramate as emulsifier.

Example 11

The weed activity of the agent (A) of the present invention against aquatic weeds was compared to the activity of copper sulfate complex with diethanolamine and triethanolamine (B, trade name Cutrine) known from U.S. Patent No. 2,734,028. The agent of the invention contained a complex of copper (II) sulfate and ethylenediamine. The copper content of both agents was the same (7.0 wt%). Treatment results were evaluated at 2, 4, and 6 weeks after treatment and the results are presented in the following table. The agent contained the carrier and emulsifier named in Example 7 in the ratios given therein. The results clearly show that the effect of the agent according to the invention far exceeds that of the known agent.

Similar results are obtained when any agent of the invention is used to control water weeds.

% herbicidal effect Mounting Composition of the active substance Copper content (ppm) Najadaceae Hydrilláé 2 4 ^{6 2} 4 6 seven seven THE copper (II) sulfate / EDA (7.0% Cu) 0.25 99 100 100 100 100 100 0.5 98 100 99 100 100 100 0.75 98 99 100 100 100 100 1.0 100 100 100 100 100 100 B copper (II) sulfate / TEA / DEA 0.5 18 15 40 13 28 28 (7.0 S Cu) 0.75 37 35 47 40 60 93 (Cutrine) 1.0 52 75 85 82 93 95 2.0 40 85 98 80 94 98

ED A = ethylenediamine

TEA / DEA = triethanolamine / diethanolamine

Claims (13)

CLAIMS 1. An agent for controlling algae and aquatic weeds, characterized in that the active ingredient is a copper (II) salt, a complexing agent and an amine of the formula I, in which R _l R _2, R and R ₄ are each independently hydrogen or methyl, 40 R 5 is _{a C} 2 -C 4 alkylene group and n is a 1-4 complex, the molar ratio of amine to complex copper (II) salt is 1: 1 to 10: 1 and the copper content is 1 to 12% by weight, carrier, preferably xylene and / or a surfactant, preferably sorbitan monooleate. An agent according to claim 1, characterized in that it is a water-dilutable concentrate. An agent 50 according to claim 1 or 2, wherein the pH is between 6 and 12. 4. An agent according to claim 3, wherein the pH is between 8 and 12. 5. The agent of claim 3, wherein the pH is between 9 and 11.5. 55 6. An agent according to any one of claims 1 to 5, characterized in that it contains 6 to 10% by weight of copper. 7. The composition of claim 6 wherein the copper content is from 7 to 8.5% by weight. 8. An agent according to claim 6 or 7, wherein the molar ratio of the amine of formula I to the copper (II) salt is 1: 1 to 5: 1. 9. The agent of claim 8, wherein the molar ratio of the amine of formula I to the copper (II) salt is 1: 1 to 3: 1. 10 embodiment by any one of the preceding claims, characterized in that the complex I _R} amine component is of the formula 2 or 3 carbon alkylene group and n is the first 11. The agent of claim 10, wherein the amine of formula I is N-methylethylenediamine or 1,2-propylene diamine. 12. The agent of claim 10, wherein the amine of formula I is ethylenediamine. 13. An embodiment of the agent according to any one of the preceding claims, wherein the copper (II) complexing agent is copper (II) sulfate pentahydrate.